Recently, facilely designable metal-organic frameworks have gained attention in the construction of photothermal conversion materials. Nonetheless, most of the previously reported photothermal conversion metal-organic frameworks exhibit limited light absorption capabilities. In this work, a distinctive metal-organic framework with heterogeneous periodic alternate spatial arrangements of metal-oxygen clusters and perylene-based derivative molecules was prepared by in situ synthesis. The building blocks in this inimitable structure behave as both electron donors and electron acceptors, giving rise to the significant inherent charge transfer in this crystalline material, resulting in a narrow band gap with excellent panchromatic absorption, with the ground state being the charge transfer state. Moreover, it can retain excellent air-, photo-, and water-stability in the solid state. The excellent stability and broad light absorption characteristics enable the effective realization of near-infrared (NIR) photothermal conversion, including infrequent NIR-II photothermal conversion, in this perylene-based metal-organic framework.